Cobalt-based catalysts have been identified for effective CO oxidation, but their activity is limited by molecular O2 and interfacial oxygen passivation at low temperatures. Optimization of the d-band structure of the cobalt center is an effective method to enhance the dissociation of oxygen species. Here, we developed a novel Co/FeOx catalyst based on selective cationic deposition to anchor Co cations at the defect site of FeOx, which exhibited superior intrinsic low-temperature activity (100%, 115 °C) compared to that of Pt/Co3O4 (100%, 140 °C) and La/Co2O3 (100%, 150 °C). In contrast to catalysts with oxygen defects, the cationic Fe defect in Co/FeOx showed an exceptional ability to accept electrons from the Co 3d orbital, resulting in significant electron delocalization at the Co sites. The Co/FeOx catalyst exhibited a remarkable turnover frequency of 178.6 per Co site per second, which is 2.3 times higher than that of most previously reported Co-based catalysts. The d-band center is shifted upward by electron redistribution effects, which promotes the breaking of the antibonding orbital *π of the O═O bond. In addition, the controllable regulation of the Fe-Ov-Co oxygen defect sites enlarges the Fe-O bond from 1.97 to 2.02 Å to activate the lattice oxygen. Moreover, compared to CoxFe3-xO4, Co/FeOx has a lower energy barrier for CO oxidation, which significantly accelerates the rate-determining step, *COO formation. This study demonstrates the feasibility of modulating the d-band structure to enhance O2 molecular and interfacial lattice oxygen activation.
Keywords: CO catalytic oxidation; Fe–O–Co structure; d-band structure; lattice oxygen modulation; molecular O2 activation.